EP0947243B1 - Mittel mit Copolymerisaten aus N-Vinylcarbonsäureamiden und Monomeren mit hydrophobem Rest, und Verwendung dieser Copolymerisate - Google Patents

Mittel mit Copolymerisaten aus N-Vinylcarbonsäureamiden und Monomeren mit hydrophobem Rest, und Verwendung dieser Copolymerisate Download PDF

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Publication number
EP0947243B1
EP0947243B1 EP99106684A EP99106684A EP0947243B1 EP 0947243 B1 EP0947243 B1 EP 0947243B1 EP 99106684 A EP99106684 A EP 99106684A EP 99106684 A EP99106684 A EP 99106684A EP 0947243 B1 EP0947243 B1 EP 0947243B1
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EP
European Patent Office
Prior art keywords
vinyl
acid
carboxylic acids
monoethylenically unsaturated
cycloaliphatic
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Expired - Lifetime
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EP99106684A
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German (de)
English (en)
French (fr)
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EP0947243A2 (de
EP0947243A3 (de
Inventor
Stephan Kothrade
Anton Negele
Helmut Meffert
Axel Sanner
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/16—Amines or polyamines

Definitions

  • the present invention relates to compositions containing at least a water-insoluble ingredient and at least one copolymer from at least one N-vinylcarboxamide, at least one Monomer with a hydrophobic residue and optionally at least a copolymerizable monomer. It also affects use these copolymers as solubilizers and as protective colloids, especially for the stabilization of oil-in-water emulsions.
  • No. 3,207,656 describes the use of water-soluble copolymers which are based on esters of acrylic acid or methacrylic acid which carry cationic sulfonium ions.
  • C 1 -C 10 alkyl esters of acrylic acid and methacrylic acid, C 1 -C 4 alkyl vinyl esters or N-vinyl carboxamides can also be used to build up corresponding copolymers.
  • Copolymers are known from EP 0 251 182 which, in addition to N-vinylformamide and N-vinylamine also acrylonitrile units and optionally small proportions of acrylamide and acrylic acid units contain. These copolymers are also found in the paper industry Application.
  • EP 0 216 387 describes copolymers which, in addition to N-vinylformamide, also contain other ethylenically unsaturated monomers, such as vinyl acetate, vinyl propionate, C 1 -C 4 -alkyl vinyl ether, N-vinylpyrrolidone, acrylic acid amide or C 1 - C 18 alkyl esters of acrylic and methacrylic acid can contain. Partial or complete hydrolysis of these copolymers also leads to copolymers which contain vinylamine units.
  • DE 36 20 065 also discloses polymers for the production of paper, cardboard and cardboard which are based on N-vinylcarboxamides or cyclic N-vinylamides, such as N-vinyllactams.
  • These polymers which can be used as dewatering, retention and flocculants, can also (meth) acrylamide, (meth) acrylonitrile, C 1 -C 18 alkyl esters of acrylic and methacrylic acid, C 1 -C 4 alkyl vinyl esters or C 1 -C 4 - Contain alkyl vinyl ether.
  • WO 82/02073 describes copolymers which, in addition to N-vinylformamides, may contain further comonomers, such as acrylamide, (meth) acrylonitrile, (meth) acrylic acid or C 1 -C 6 -alkyl esters of acrylic or methacrylic acid. Such copolymers are used as friction reducers for acids in oil and gas production.
  • JP-A-84/039399 describes hydrolyzed N-vinylcarboxamide containing copolymers for dewatering sludges.
  • a cationic polymerization process for the synthesis of N-vinylformamide or oligomers or polymers containing N-vinylacetamide is known from DE 43 22 854.
  • vinyl ethers especially butyl vinyl ether, styrene, ⁇ -methylstyrene, Isobutylene and alkyl substituted olefins called.
  • These polymers are said to be hydrolyzed, partially hydrolyzed or unhydrolyzed form in adhesives, binders where Water treatment, papermaking, oil and mineral extraction, body care and biomedicine.
  • polymers which can be used in cleaning processes are described in EP 0 753 570.
  • these polymers may optionally contain further comonomers, such as C 1 -C 18 -alkyl vinyl esters, C 1 -C 4 -alkyl esters of acrylic or methacrylic acid or optionally with C 1 - C 10 radicals substituted acrylic or methacrylamides.
  • the use of these polymers is intended to prevent the dirt from settling again after cleaning and to give the cleaned object a certain resistance to dirt.
  • WO 96/03969 and US 5,478,533 describe hair care products containing an N-vinylformamide homopolymer or a copolymer of N-vinylformamide units and a further vinyl monomer selected from styrenes, C 1 -C 18 -alkyl esters of acrylic and methacrylic acid, C 1 -C 18 alkyl vinyl esters, NC 1 -C 12 -N'-C 1 -C 18 alkyl substituted acrylic and methacrylamides, esters of fumaric, itaconic and maleic acids, vinyl ethers such as methyl vinyl or isobutyl vinyl ether, hydroxy -functionalized acrylates and methacrylates, acrylamide, cyclic amides and other monomers.
  • Such polymers are said to impart hair-setting and hair-conditioning properties to the hair care products.
  • the present invention has for its object means for To provide the better solubilization of water-insoluble Enable ingredients.
  • alkyl includes straight-chain or branched alkyl groups, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, lauryl, myristyl, cetyl, Stearyl, arachinyl, behenyl or lignoceryl.
  • alkenyl includes straight-chain or branched, simple or polyunsaturated alkenyl groups, such as palmitoleyl, Oleyl, linoleyl, linolenyl or arachidonyl.
  • cycloalkyl embraces cycloalkyl radicals such as e.g. cyclopropyl, Cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
  • monoethylenically unsaturated C 3 -C 8 carboxylic acid encompasses both mono- and dicarboxylic acids. These include, for example, acrylic acid, methacrylic acid, dimethacrylic acid, ethacrylic acid, maleic acid, citraconic acid, methylene malonic acid, allylacetic acid, vinyl acetic acid, crotonic acid, fumaric acid, mesaconic acid or itaconic acid. Of these, (meth) acrylic acid or maleic acid are preferred. The notation “(meth) acrylic” is used collectively for "methacrylic" and "acrylic".
  • neutralized acids are understood to be salts which are obtained by reacting the acids with bases.
  • alkali metal or alkaline earth metal bases for example sodium hydroxide solution, potassium hydroxide solution, sodium or potassium carbonate, sodium or potassium hydrogen carbonate, magnesium oxide, calcium hydroxide, calcium oxide, gaseous or aqueous ammonia, or amines, for example triethylamine, ethanolamine, diethanolamine, triethanolamine, morpholine, diethylenetriamine or tetraethylene pentamine, preferred.
  • esters and amides of monoethylenically unsaturated dicarboxylic acids the half esters or half amides also belong.
  • aliphatic radical encompasses straight-chain or branched, saturated or mono- or polyunsaturated, and / or mono- or polycarbonate groups interrupted independently by groups selected from O, S, CO or SO 2 .
  • cycloaliphatic radicals which additionally have at least one cyclic structural unit.
  • Monomers are used to construct the copolymers according to the invention
  • the N-vinylcarboxamide of the formula I is preferably under N-vinylformamide, N-vinyl-N-methylformamide, N-vinyl-N-ethylformamide, N-vinyl-N-propylformamide, N-vinyl-N-isopropylformamide, N-vinyl-N-n-butylformamide, N-vinyl-N-isobutylformamide, N-vinyl-N-t-butylformamide, N-vinyl-N-n-pentylformamide, N-vinyl-N-n-hexylformamide, N-vinyl acetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinyl propionamide, N-vinyl-N-methyl propionamide and N-vinylbutyramide selected.
  • N-vinylformamide and N-vinyl-N-methyl
  • N-vinyl carboxamides are used.
  • Monomers B) with a hydrophobic residue, with vinyl carboxamides of the formula I are copolymerizable, in amounts of 1 to 95 % By weight, preferably 3 to 50% by weight and in particular 5 to 40 % By weight.
  • the monomers B) are according to the invention selected from b1) -b4) as defined in claim 1.
  • the monomers B) are generally long-chain, aliphatic or cycloaliphatic radicals with at least 8, preferably up to 30 and in particular with 12 to 24 carbon atoms.
  • alkyl or alkenyl residues in particular n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, lauryl, myristyl, Cetyl, stearyl, behenyl or oleyl are preferred.
  • the cycloaliphatic radicals are preferably C 5 -C 8 cycloalkyl radicals, in particular cyclohexyl or cycloheptyl, which are substituted by C 1 -C 4 alkyl.
  • T-Butylcyclohexyl is very particularly preferred.
  • Esters of monoethylenically unsaturated C 3 -C 8 carboxylic acids with aliphatic or cycloaliphatic C 8 -C 30 alcohols, preferably C 12 -C 24 alcohols, are among the preferred monomers with a hydrophobic radical, the aliphatic or cycloaliphatic alcohols being different from the corresponding ones , derived above, aliphatic or cycloaliphatic radicals. These are preferably the primary monoalcohols of such residues.
  • Amides of monoethylenically unsaturated C 3 -C 8 carboxylic acids with primary or secondary amines with at least one of the aliphatic or cycloaliphatic C 8 -C 30 , preferably C 8 -C 18, radicals defined above are also preferred monomers with a hydrophobic radical.
  • Primary amines lead to N-monosubstituted amides, while secondary amines lead to N, N'-disubstituted amides.
  • the secondary amines can be two, also different, aliphatic or cycloaliphatic C 8 -C 30 , preferably C 8 -C 18 radicals, or only one of these radicals together with an aliphatic or cycloaliphatic radical having 1 to 7 carbon atoms, in which it is is preferably one of the C 1 -C 7 alkyl radicals defined above.
  • Monomers B) are the (meth) acrylate esters octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, Decyl (meth) acrylate, lauryl (meth) acrylate, myristyl (meth) acrylate, Cetyl (meth) acrylate, stearyl (meth) acrylate, oleyl (meth) acrylate, behenyl (meth) acrylate and t-butylcyclohexyl (meth) acrylate and the (Meth) acrylamides N-stearyl (meth) acrylamide, N-octyl (meth) acrylamide, N, N-dioctyl (meth) acrylamide, N-cetyl (meth) acrylamide, N-dodec
  • Vinyl esters of aliphatic or cycloaliphatic C 8 -C 30 , preferably C 8 -C 18 carboxylic acids also belong to the preferred monomers with a hydrophobic radical.
  • the aliphatic or cycloaliphatic carboxylic acids are derived from the corresponding aliphatic or cycloaliphatic radicals defined above, preferably monocarboxylic acids.
  • Examples of suitable, with N-vinylcarboxamides of the formula I. copolymerizable monomers B) are therefore also the vinyl esters of octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, lauric acid, Tridecanoic acid, myristic acid, palmitic acid, stearic acid, Arachic acid or behenic acid or oleic acid.
  • vinyl ethers of aliphatic or cycloaliphatic C 8 -C 30 preferably C 8 -C 18 alcohols.
  • Monomers with a hydrophobic radical are also preferred.
  • the aliphatic or cycloaliphatic alcohols are derived from the corresponding aliphatic or cycloaliphatic radicals defined above, which are preferably monoalcohols.
  • Examples of suitable, with N-vinylcarboxamides of the formula I. copolymerizable monomers B) are therefore also the vinyl ethers of octyl alcohol, 2-ethylhexyl alcohol, 1-nonyl alcohol, decyl alcohol, Undecyl alcohol, lauryl alcohol, tridecyl alcohol, myristyl alcohol, Palmityl alcohol, stearyl alcohol, arachinyl alcohol or behenyl alcohol or oleyl alcohol.
  • Monomers C) are used.
  • Acrylic acid, methacrylic acid, maleic acid, N-vinylpyrrolidone and N-vinylcaprolactam are among the copolymerizable described above Monomers C) are particularly preferred.
  • copolymers are prepared by known processes, for example, the solution, precipitation, suspension or reverse suspension polymerization, or the emulsion or reverse emulsion polymerization using compounds, which form radicals under polymerization conditions.
  • linear polymers known from EP 0 071 050 contain the copolymerized vinyl formamide units. These polymers are made by homopolymerization.
  • Copolymers of N-vinylcarboxamides and other monoethylenic unsaturated compounds such as acrylic acid, acrylic acid esters, Vinyl acetate, N-vinyl pyrrolidone or acrylonitrile are also described in the literature. They are also known modified by the action of acids or bases Polymers in which the carboamide groups are wholly or partly eliminated from the polymerized N-vinylcarboxamides can be and in which the copolymerized comonomers optionally are hydrolyzed.
  • the EP 0 are exemplary here 216 387, EP 0 251 182, EP 0 528 409, WO 82/02073, JP 84/033302, JP 84/039399, EP 0 337 310 and DE 43 22 854 called.
  • the polymerization temperatures are usually in the range from 30 to 200 ° C, preferably 40 to 100 ° C.
  • Suitable initiators are for example azo and peroxy compounds as well the usual redox initiator systems, such as combinations of hydrogen peroxide and reducing compounds, for example Sodium sulfite, sodium bisulfite, sodium formaldehyde sulfoxylate and hydrazine.
  • the copolymers have K values of at least 7, preferably 10 to 30. However, the polymers can have K values up to 300.
  • the K values are in aqueous solution at 25 ° C at concentrations, which are between 0.1% and 5% depending on the K value range, according to H. Fikentscher, Cellulose-Chemie, Vol. 13, 58 - 64 and 71 bis 74 (1932).
  • Water-insoluble ingredients are understood according to the invention Substances that are not miscible with water in all proportions are. Often, these cannot be effectively for the Dissolve effectiveness required concentrations. It deals are mainly substances whose solubility in water is less than 30 wt .-% and in particular less than 20 wt .-% at 25 ° C.
  • the present invention is particularly advantageous for ingredients with solubilities in water of less than 5% by weight and especially less than 1% by weight.
  • the water-insoluble ingredients according to the invention include Active ingredients and auxiliaries for pharmaceutical and cosmetic use on humans and animals, for plant treatment or for Nutrition technology.
  • water-insoluble pharmaceutical active ingredients are fat-soluble vitamins and provitamins, especially vitamins of E group, protease inhibitors, such as ritonavir, indinavir or saquinavir, Amlodipine, astaxanthin, astemizole, beclomethasone, benzocaine, Betamethasone, bromazepam, bromocriptine, budesonide, camphor, Captopril, carbamazepine, carboplatin, chloramphenicol, Chlorhexidine, cyclosporin, cisplatin, clarithromycin, clonazepam, Clotrimazole, clozapine, codeine, desogestrel, dexamethasone, diazepam, Digoxin, dihydrocodeine, dihydroergotamine, dihydroergotoxin, Ephedrine, epinephrine, erythromycin, estradiol, ethinyl estradiol,
  • Active ingredients and auxiliaries for cosmetic use relate in particular skin care, hair cosmetics, nail care or oral hygiene.
  • Examples include perfume oils, ethereal Oils, essences or oily bath additives.
  • active substances for treating plants are pesticides, Herbicides, fungicides or insecticides especially for spray or Watering broths such as strobilurins, vinclozolin or epiconazole.
  • the active ingredients and adjuvants for nutritional technology include Food supplements, for example for dietetic foods, Food colors such as carotenoids or feed additives for animal nutrition.
  • the agents according to the invention are therefore primarily pharmaceutical and cosmetic formulations, formulations for plant treatment and nutritional technology Purposes. These are preferably liquid (also as a spray), solid or semi-solid. With regard to liquid and especially aqueous The invention offers particular advantages in formulations.
  • solid dosage forms such as powder, powder, granules, tablets, Coated tablets, capsules, suppositories or vaginal dosage forms
  • semi-solid dosage forms such as ointments, creams, hydrogels, pastes or plasters
  • liquid pharmaceutical forms such as solutions, emulsions, in particular oil-in-water emulsions, suspensions, for example Lotions, injection and infusion preparations, eye and ear drops.
  • Cosmetic products include, for example, skin care products, such as skin cleansing agents, for example soaps or bath preparations, Skin care products, usually emulsions and in particular Oil-in-water emulsions, decorative personal care products for face, eyes, lips and nails, intimate and foot care products, Light stabilizers, skin tanning agents, depigmenting agents, insect repellents, deodorants, antiperspirants, Hair removal and shaving preparations, fragrances, dentifrices and oral care preparations or hair treatment agents, for example for washing, Maintaining, shaping, setting, bleaching or coloring the Hair.
  • skin care products such as skin cleansing agents, for example soaps or bath preparations
  • Skin care products usually emulsions and in particular Oil-in-water emulsions
  • decorative personal care products for face, eyes, lips and nails intimate and foot care products
  • Light stabilizers skin tanning agents, depigmenting agents, insect repellents, deodorants, antiperspirants, Hair removal and shaving preparations, fragrances, dentifrices and oral care
  • Plant treatment agents can be, for example, in the form of directly sprayable solutions, powders, suspensions, also high-proof aqueous suspensions or dispersions, emulsions, Pastes, dusts, sprinkles or granules for spraying, Nebulization, dusting, scattering or pouring are present.
  • auxiliary substances contained in the usual amounts.
  • these include, for example Antioxidants, anti-irritants, antistatic agents, bath additives, Chelating agents, disinfectants, dispersants, coating aids, Emulsifiers, emulsion stabilizers, if appropriate ethoxylated and / or propoxylated fatty alcohols, fatty amines, fatty amine oxides, Fatty acid alkylolamides, fatty acid esters, fatty acids, Humectants, film formers, gel formers, odor masking agents, Flavors, hair conditioners, hair lacquer raw materials, Hair care products, resins, skin oils, skin care products, Skin protection agents, hydrocolloids, preservatives, lip care products, Solvents, solubilizers, moisturizers, wetting agents, Neutralizing agents, mother-of-pearl gloss agents, permeation accelerators, Pigments, protein derivatives and / or hydrolyzates
  • a design in this regard is based on professional knowledge, as it is for example in Fiedler, H.P., Lexicon of excipients for pharmacy, cosmetics and related Areas, 4th edition, Aulendorf: ECV-Editio-Kantor-Verlag, 1996, is shown.
  • the compositions according to the invention contain Typically 0.05% to 20% by weight, preferably 0.1 to 10% by weight and particularly preferably 0.5 to 5 % By weight of copolymer according to the invention and 0.1% by weight to 90 % By weight, preferably 0.1 to 60% by weight, of insoluble ingredient.
  • copolymers according to the invention are outstandingly suitable Way as a solubilizer.
  • solvents are understood substances that, due to their presence, compounds practically insoluble in a particular solvent soluble or dispersible in this solvent, i.e. make suspendable or emulsifiable.
  • the copolymers according to the invention are suitable as solubilizers for water-insoluble ingredients, especially for the above Active ingredients or auxiliaries for pharmaceutical or cosmetic Application, for plant treatment or for nutritional technology.
  • the copolymers according to the invention act as permeation accelerators, that is to make it easier to overcome permeation barriers, like skin and mucous membrane. Many also need it of the above means of stabilizing Liquid / liquid and / or solid / liquid mixtures in which the respective Phases not miscible or spontaneously not homogeneous Mix result.
  • the copolymers according to the invention are therefore found also used as stabilizers of dispersions, i.e. Emulsions, especially oil-in-water emulsions, or suspensions. In this capacity they are often called Protective colloids called.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Cosmetics (AREA)
  • Medicinal Preparation (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP99106684A 1998-04-03 1999-04-01 Mittel mit Copolymerisaten aus N-Vinylcarbonsäureamiden und Monomeren mit hydrophobem Rest, und Verwendung dieser Copolymerisate Expired - Lifetime EP0947243B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19815127 1998-04-03
DE19815127A DE19815127A1 (de) 1998-04-03 1998-04-03 Mittel mit Copolymerisaten aus N-Vinylcarbonsäureamiden und Monomeren mit hydrophobem Rest, und Verwendung dieser Copolymerisate

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EP0947243A2 EP0947243A2 (de) 1999-10-06
EP0947243A3 EP0947243A3 (de) 2000-02-02
EP0947243B1 true EP0947243B1 (de) 2004-10-27

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US (1) US6939912B2 (es)
EP (1) EP0947243B1 (es)
JP (1) JP4233170B2 (es)
AT (1) ATE280635T1 (es)
CA (1) CA2265073A1 (es)
DE (2) DE19815127A1 (es)
ES (1) ES2229572T3 (es)

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JP4468180B2 (ja) * 2002-12-02 2010-05-26 ビーエーエスエフ ソシエタス・ヨーロピア 農業技術分野における補助剤および作用剤としてのｎ−ビニルアミド系コポリマー
JP5315231B2 (ja) * 2006-03-15 2013-10-16 ハンツマン ペトロケミカル エルエルシー 農業用分散剤として有用なポリエーテルアミンのコームポリマー誘導体
MX298466B (es) * 2006-05-18 2012-04-23 Hercules Inc Productos de adicion de michael como aditivos para el papel y la fabricacion de papel.
WO2007141182A2 (de) * 2006-06-07 2007-12-13 Basf Se Verwendung von vinylacetat-sulfonat-copolymeren als solubilisatoren für in wasser schwerlösliche verbindungen
BRPI0719399B8 (pt) * 2006-11-30 2016-06-28 Basf Se formulação, uso de copolímero, métodos para combater insetos prejudiciais e/ou fungos fitopatogênicos, para controlar vegetação indesejada e para melhorar a saúde das plantas
JP5323715B2 (ja) * 2006-11-30 2013-10-23 ビーエーエスエフ ソシエタス・ヨーロピア １−ビニル−２−ピロリジノンコポリマーを含む農薬製剤
AR064292A1 (es) 2006-12-12 2009-03-25 Commw Scient Ind Res Org Dispositivo mejorado para almacenamiento de energia
AR067238A1 (es) 2007-03-20 2009-10-07 Commw Scient Ind Res Org Dispositivos optimizados para el almacenamiento de energia
BRPI0813749A2 (pt) * 2007-07-06 2015-01-06 Basf Se Uso de homo- copolímeros p, composição de composto ativo, preparação de composto ativo aquosa, uso de uma composição de composto ativo, processo para a preparação de uma dispersão aquosa de compostos ativos orgânicos fracamente solúveis em água, e, dispersão aquosa de compostos ativos orgânicos fracamente solúveis em água
JP5485895B2 (ja) * 2007-09-27 2014-05-07 ビーエーエスエフ ソシエタス・ヨーロピア 浸透移行性増強剤
US9450232B2 (en) 2009-04-23 2016-09-20 Commonwealth Scientific And Industrial Research Organisation Process for producing negative plate for lead storage battery, and lead storage battery
JP5715630B2 (ja) 2009-08-27 2015-05-07 コモンウェルス サイエンティフィック アンド インダストリアル リサーチ オーガナイゼーション 蓄電装置及びその電極
JP5797384B2 (ja) 2009-08-27 2015-10-21 古河電池株式会社 鉛蓄電池用複合キャパシタ負極板及び鉛蓄電池
JP5711483B2 (ja) 2009-08-27 2015-04-30 古河電池株式会社 鉛蓄電池用複合キャパシタ負極板の製造法及び鉛蓄電池
JP2012133959A (ja) 2010-12-21 2012-07-12 Furukawa Battery Co Ltd:The 鉛蓄電池用複合キャパシタ負極板及び鉛蓄電池
CN105542735B (zh) * 2015-12-22 2018-07-27 中国科学院广州能源研究所 一种水合物动力学抑制剂及其应用

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JP2000001595A (ja) 2000-01-07
US20030013800A1 (en) 2003-01-16
ES2229572T3 (es) 2005-04-16
DE19815127A1 (de) 1999-10-07
CA2265073A1 (en) 1999-10-03
EP0947243A2 (de) 1999-10-06
EP0947243A3 (de) 2000-02-02
US6939912B2 (en) 2005-09-06
ATE280635T1 (de) 2004-11-15
DE59910925D1 (de) 2004-12-02
JP4233170B2 (ja) 2009-03-04

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